Peroxide of hydrocarbon and process of making the same



Oct. 3o, 1929.y

9 1,689,599* A. `s. RAMAGE PEROXIDE op mnocmon AND PRocEss oF MAxgNG THE sAME Filed April 27, 1925 admirably suited as "a thinner' L'ate its'nasoent oxygen at once when treated rumen ou; 3o. 192s.

annnnn s. MIAGE.. or Dunmore, Mrcniean.

runen on mnnocnanonfnun rnocnss ora'xme 'run sans.

application mea A'prn 27. 1925. serial nu. -26,2955.

...Thisfinvention relates to the 1 production of peroxides of'funsaturated h drocarbons such as o'lens, cyclo-diolefins, cyclo-.paraftins, -naphthenuesy etc., and mixtures thereof,

5 such as are produced 'for instance by the processes vdisclosed ,in United States. Patents No. 1,224.78? and No. l,409,404, 'and the Well known petroleum cracking processes.

The process consists generally in contact l0 ing ozoniae'd or ozone or a gas' containing ozone fvvith the hydrocarbons at suitable tem" r `The accompanying drawing 2--ofthe process. w l5. For example, an unsaturated hydrocarf bonmixturersujeh as those produced bythe processes of the patents referred to is preferably distilled vand cut intot-wo `ractions,

' v onefraotion 'having an end point not over 150 C. and.. the secondfr'ac'tion being the heavier-product, distilling-between 150 C.

' and 200 C. -The irstfractionis preferably. ozonized by blowing ozone or ozonized air through it While it is held at a temperature is a flow sheet l5 bf 40 C. 'Practically 80%"of the fraction passes" over asa dense, vvhit'e` vapor which? is subjected to condensation in anysuitable manner, about seven-eightlis of itcondensing the very light uncondensible portione being i a0 passed'through an ordinary wash yoil .sys-

tem using. heavy Wash oil, fromwhich washl .oil a very light product .can befrecovered treated.' vThus I obtain three products',-f`.`

20%' of residue which will be described herey inafter, 10% from the wash oil of a light product which, provided the starting ma' terial :is free from saturated roducts,'i s or Celluloid varniSheS, and 70% of an'organic peroxide twhich in' Contact withl moisture; liberates nascent oxygen. 4This o gen content can be tested by the usual 'acidlulated' potassium iodide solution 'and estimation of the iodine .liberated andoalculated vto oxygen. `It will f'be found that a peculiar characteristic of 'this organicperoxide is that it does not liber- Ib 'with water, but does so gradually I'over a "riod of 36 hours. The light. product rom' 'the wash. oil, duringv distlllationf liberates an"enori nous amount of gaseous' lfirst fraction and simil before,

lead, zinc oxid or even r 'results stated above are obtained -TheA second fraction boiling vbetvveen l50- 200 C. is added to the residue fromf-the first fraction andthe mixture isfofzonizedas 1n the case of the `ilfirst fraction', but at a temperature of about 7080o C. or even n@ hugher.l Similar products distill oand I prefer tosto'p vthe ozonization ata point where the residue is about 410% of the oxygn at a temperature 4of about 40 to quantity of 4material-treated. AThis residue is a thicl, varnish-like `body and dries 5 rapidly,v giving a tough,phard film, The peroxide or ozonized product which has been vaporl'zed and condensed and which amounts J, toabout 50% of the second fraction is added to the peroxide or ozonized product from -the 73.

arly the product from the washoil is added .to t e corresponding product from the'frst fraction. y

l The peroxide or ozonized product from the two fractions which amounts to about`fi0% 75 of the'material .treated is extremely well.

n placeof turpentine, d ue to the -fact that in mixtureswith drying 911s 1t will dry, for instance raw'linseed oil 1n one-third the time that turpentine will, 80 due to its oxidizing action. Drying alone, which will takel place in about 6 hours, 'it will produce a film which is toughand hard.

It is also applic-able for increasing the power of gasoline or other. motor spirit (with which: it' 1s perfectly. miscible.)v due to the liberation of its' oxygen.

Should increased drying speed be desired,- the unsaturated hydrocarbons may be mixed or the products maybett-cated afterwardsfwith alittle black oxid of manganese', MnO2, which will materially. increase the drying speed.4 The lresidue of the ozoniz mg operation may be used as a varnishv or 'as a llnseed oil substitute and has the pecuo5 liar advantage that it can ,be ixed with ac tive pi ents such as basic chromes, white ed lead; Without' livering or becoming hard It can be readily `seen that any desired vloo degree of varnish may be obtained by the degree of 'ozonization For instance, Ithe.

by -3 :to

4 hours of ozonization with air containing from 3 to 4% of ozone; and if the ozoniia- 1054 tionfis continued to 5 or 6 hours, the residue 2 l incassati@Y withwash oil, and recovering a product om l dleft in the still becomes a semi-solid resinwhich may be used as" a varnish gumto temper the hardness of yfossil gums.

1. Process which comprises ,passing ozonized airthrough a body of li uid containing unsaturated hydrocarbons, s jecting the resulting gases and vapors to condensation, contacting the uncondensed gases and va rs the wash oil by distillation.

2. Process which comprises separating a hydrocarbon mixture containing unsatuV Y rated hydrocarbons, into a higher fraction and a lower to condensation,

'25 ,from the mixin said first ozonized residue' with said.

high oiling fraction, passing o zonized resthroughthe mixture of said first lidue and high boiling fraction, thereby pro A ducingfa second ozoniz-ed residue and asecond batch of gases and vapors, subjecting said second batch of gasesand vapors to condensation," thereby producing ya second condensate ,and a second batch of. uncon-A densed gases and'fvapors, mixing said second condensate with said-'first condensate, con` tacting said second batch of uncondensed gases and vapors with a wash' oil, recovering -4 a SecQnd-jwash oil product from the wash oil mixture by distillation, and mixing said sec-y ondvwash oil product with said first wash oil product. t 'f 3. Process which comprises contacting ,a

- mixtureofilnsaturated hydrocarbons with fa. as containingwozon'e at avtemperature sufcient to vaporize aportion at least of the* resulting: peroxidesf of th hydrocarbons, l condensing a portionof the va oxides and collecting -50 orizedper'- v the con ensate, ,and

l contactingfsthe'remainder of the vaporiied peroxidesiwith an tabsorbent oil.

" 4. Process which comprises passing'ozonized -air through a'liquid'-hydrocarbon n/iixrecovering a. first was oil product'.

` gases bon mixtures.

drying aproperties and 1i ra turecomprising unsaturated -h at a temperature fabout 40 said mixture having an end point of 15.090., condens# ing a portieri .of the resulting gases and vapors av d absorbing the uncondensed gases and vapors in an oil.

5` Process which comprises .ozonizing a drocarbons y liquid mixture of hydrocarbons comprising unsaturated hydrocarbons and having a-n end l,

point of about 150 C. 'at a temperature of4 pxroduci-ngan ozonized c about 40 C., thereby residue and a'first bat ofl gases andva ors condensing` a. portion o-.said first I'b at'c 9o gases andiaPOlS, thereby; Iii-dwing a first organic'penoxide condensate` and ,aiirstbatch i ofxuncondensed gases and vapors, absorbin asid first batch of uncondensed gases an c vapors in a wash oil, recovering a. first light solvent Vliquid from the -wash oilimixture .l

with a mixture of'hydrocarbons comprising (unsaturated hydrbcarbons and boiling bedistillation, mixing said ozonized residue tween 1507g'and 2009/0., ozonizing-the mixf, ture of 'said ozoniped. residue and hydro? carbo at about C., therebyproducing a var' l like residue and a second batch of i and vapors,"condensin a portion-of said second batch of gasesaii` vapors, tliereby ,producing a second organic? peroxide con-' a second batch V,of ,-uncondensed said vapors, mixing said second organic' v densate an peroxid roxide condensate, .absrbin I atch of uncondensed lgases; an vaporsii'i a e condensate with said-irst organic] ,the second a wash oil, recoverin a second 'li ht'` solvent liquid ro'm'the was o' mixture yvdistillation and mixingsaid second light solvent liquid -with said first light solvent liquid.`

be-obtained by cracking petroleu'm hylrocar-V 7 As a new product,

iiiquidi'aiiafe i organic' peroxides *obtainable bypassin"f.--f

ozoiiized air througha'liqiiid "mixture o cracked ej resulting gases vand vapors to` condensation, 'the resultin' liquid. having slowly in the presence of water.

petrolgum hydrocarbons ,and subs t ,A

6: Process which comprisesf'zoni'zing al 'p liquid'finixturesi hydrocarbons-such as 'may ion @sexism Intestimony whereof, I aix my' signature.l 

